Multiple compartment processing pod



.Jan. 16, 1968 R. w. BECKER I 3,364,025

MULTIPLE COMPARTMENT PROCESSING POD Filed. May 23, 1966 COMPAI? TME/VT c COMPARTMENT B COMPARTME/V r A COMPARTMENT C COMPARTME/VT B J COMPARTME/VT A RICHARD W BEG/(E7? INVEN R.

ATTORNEYS United States Patent MULTIPLE COMPARTMENT PROCESSING POD Richard W. Becker, Rochester, N.Y., assiguor to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey Continuation-impart of application Ser. No. 228,319,

Oct. 4, 1962. This application May 23, 1966, Ser.

13 Claims. (Cl. 96-29) ABSTRACT OF THE DISCLOSURE A multiple compartment processing pod having staggered closures, and a photographic product utilizing the processing pod.

This application is a continuation-in-part of US. Application Ser. No. 228,319, filed Oct. 4, 1962, now abandoned.

This invention relates to a photographic process wherein photographic solutions are applied from a pod-type container to an exposed light-sensitive emulsion in order to convert a latent image thereon into a visible image. More particularly, this invention relates to a multicompartment pod-type container having staggered closures.

In the pod-type photographic process, it is customary to contain a photographic solution in a single compartment pod. In the event that more than one solution is used, separate pods are employed so that the solutions are applied in sequence. In this way, separate solutions are prevented from reacting with each other until needed. Typical photographic solutions in these processes include alkali, developing agents, sodium thiosulfate, or other silver halide solvents, development accelerators, antifoggants, and special addenda, e.g., /3-phenylethyl-a-picolinium bromide.

By including some of these constituents in a single compartment pod, there may be a problem of instability or decomposition of one or more of the constituents due to the highly alkaline environment or because of interactions between the constituents. Moreover, it is often desirable to apply the constituents as a mixed solution to realize their full benefits instead of applying the components in successive layers as is necessary when separate individual pods are employed. The use of sequential, single-compartment pods has the additional disadvantage of requiring a more costly and complex element requiring substantially perfect alignment between the pods in order to obtain uniformity of reaction of the constituents of the individual pods. Pod-type processes showing the sequential discharge of containers are disclosed in Land US. Patents No. 2,846,309 and 2,584,029. Photographic processes employing single-compartment pods are disclosed in Land US. Patents No. 2,559,643 and 2,634,886.

I have discovered a method of incorporating two or more components separately in a single pod having separate compartments thereby separating the solutions until needed. These pods have at least one set of closures which are staggered permitting sequential deposition of the contents of each compartment. Since the photographic constituents are all present in a single, multiple-compartment pod, greater uniformity of reaction is obtained as opposed to the sequential use of a variety of single-compartment pods.

One object of this invention is to provide one or more compartment separators in a single pod so that compartments are formed each of which contain a separate photographic solution. Another object is to provide a process of applying a mixed solution in a pod-type process instead of a sequential application of two or more components in layer form. An additional object is to provide an improved pod which causes the segregated components therein to mix together as they flow onto the photographic emulsion. A further object is to provide an improved pod having compartments with staggered closures so that the components can be mixed in a sequential manner. A still further object is to provide a method of depositing processing components in superimposed layers.

The accompanying drawing illustrates one embodiment of my invention. FIGURE 1 is a exaggerated sectional view of a photographic element containing a single pod having two compartments with staggered closures. FIG- URE 2 illustrates a much more enlarged sectional view of a single pod having two compartments with staggered closures. A receiving sheet 13 carries thereon a container 16 containing therein the photographic solutions for developing the photographic emulsions. A photosensitive layer 11 coated on the support 10 is super-imposed over the receiving sheet and the container. The support 10 is transparent so that the light-sensitive coating can be exposed through the support but other supports may be used, such as paper, and the like, which are opaque.

The container 16 is divided into two compartments 14 and 15, separated by a compartment separator 17. In one embodiment, the container is made of cellulose acetate and has staggered breaking edges on the side of the pod facing toward the rollers used in the pod-type photographic process.

FIGURE 3 shows an end view of a single pod having three compartments and showing the staggered edges. In one embodiment, compartment A might then contain the developer agents, compartment B, the alkaline material, and compartment C, the silver halide solvent. Alternatively, the alkaline material, the silver halide develop ing agents and the silver halide solvent could be distributed between compartments A and B and compartment C would then contain a print stabilization agent, such as a resin or an ultraviolet absorber or a development arrester, such as Z-mercaptobenzoxazole. More than three compartments could be utilized if desired.

FIGURE 4 is an end view of a single pod having staggered closures on both sides. It may be desirable to include a solvent in one compartment separate from the developing composition. Moreover, if a sparingly soluble lead salt is utilized to obtain improved contrast, it should be added from a separate compartment, since it tends to coagulate some of the film forming materials used in the liquid composition. In one embodiment of the present invention, the developing agents can be present in compartment A, the alkaline material and silver halide solvent in compartment B, and the lead salt in compartment C of the pod illustrated in FIGURE 4.

The sheets forming the compartments of FIGURE 3 are sealed with the seal at the closure facing away from the rollers being made weaker than the other closure seals. Thus, when the multiple compartment pod is subject to pressure, the pressure is transmitted directly to the container and the liquid is released sequentially in the compartments in the pod in a unidirectional rnanner.

By the use of different vehicles for the components carried in the compartments, the components may be applied, if desired, as separate layers on the surface of the silver halide emulsion. In this Way, the separate layers are applied in a manner similar to the layers applied 'by the multiple slot coating hopper, which is particularly useful for coating separate layers in one coating operation.

An especially useful liquid carrying container comprises a pod having lateral compartment separators forming a plurality of compartments in a superposed position with each compartment having a bottom wall, a top wall, edge closures, an anterior closure and a posterior closure, the bottom walls and top walls of the compartments being substantially larger in area than the areas of the side closures, anterior closure or posterior closure, each compartment below the top compartment having the anterior closure extending laterally beyond the anterior closure of the last uppermost compartment and each compartment having a bottom wall and a top wall larger in area than the respective bottom wall and top wall of the last uppermost compartment.

The two-compartment container is especially adaptable for the addition of an auxiliary developing agent, for example, 4-methylphenyl hydroquinone. The incorporation of this material into the developing solution prior to the time of development is unsuitable, since the solution degrades rapidly with time. The use of the multi-compartment pods is particularly suitable for use with the color diffusion transfer process disclosed in Belgian Patents 554,933 and 554,934. The application of the auxiliary developer agent and the processing solution per se as a sequential rather than a simultaneous application does not yield the maximum benefits of the auxiliary developer agent. However, by incorporating the 4-methylphenyl hydroquinone in one compartment having a low pH separate from the higher alkaline developing solution, improved results are obtained, especially in connection with color processing in which improved color saturation is obtained.

The following examples are intended to illustrate my invention but not to limit in it any way.

EXAMPLE 1 A color negative transfer coating is prepared having the following structure, as described in Becker US. Patent application Ser. No. 71,314, filed Nov. 23, 1960, or in British Patent 804,971.

Gelatin over-coat Blue-sensitive bromoiodide emulsion Yellow dye developer Gelatin interlayer Green-sensitive bromoiodide emulsion Magenta dye developer Gelatin interlayer Red-senstive bromoiodide emulsion Cyan dye developer Cellulose ester support Several samples of the above coating are exposed on an intensity scale sensitometer to white light and through Compartment A: Percent by weight Sodium hydroxide 9.0 Benzotriazole 4.0 Hydroxyethyl cellulose 3.5 B-benzyl-wpicolinium bromide 2.0 Compartment B:

Hydroxyethyl cellulose 2.5 4'-methylphenylhydroquinone 1.0 Triethyl phosphate 4.0

The single-compartment pod has both of the above component solutions admixed in a single pod.

SINGLE COMPARTMENT POD Clear Scale Time pods are held D min Dmax before transfer Red Green Blue Red Green Blue TWO-COMPARTMENT POD Fresh 22 21 30 1. 82 1. S6 2. 12 3% hours 02 22 32 1. 80 1. 84 2. 02

It can be seen from the above results that the two-compartment pod gives lower D values and higher D values after 3% hours aging than the single-compartment pod.

Receiving sheet A which is used has the following structure:

Gelatin (300 mg./sq. ft.)+poly-4-vinyl-pyridine (300 mg./sq. ft.) +1-phenyl-5-mercaptotetrazole (15 mg./ sq. ft).

White pigmented cellulose ester support.

The time of contact is 1 /2 minutes between the nega-' tive material and receiving sheet. The temperature is room temperature approximately F. and the gap between the rollers is four-thousandths of an inch.

Other mordants might be used in combination With, or substituted for, the poly-4-vinyl pyridine mordant present in receiving sheet A. Thus, it has been found that pyrazolone couplers, phenolic couplers or couplers which are open-chain compounds containing a reactive methylene group may be used individually or in mixtures dispersed in suitable coupler solvents as useful mordants. These coupler-coupler solvent mordants may be present directly in the gelatin layer on the receiving sheet or they could be present in a compartment adjacent to the developercontaining compartment in the multiple-compartment container of this invention.

Reference has been made in the above example to a multilayer element in which the yellow, magenta and cyan dye-developers were present in separate layers placed between suitably sensitized silver halide emulsion layers. It has been discovered that one or more of these dyes when suitably dispersed and coated in a gelatin layer beneath a silver halide layer may produce, when suitably processed, either a direct positive when the unoxidized dye-developers are transferred to a contiguous receiving sheet or a negative if the unoxidized dye-developers are allowed to simply diffuse into the body of the alkaline processing solution. If one dye is used, a monochromatic image is formed; if two different dyes are used, a combination color is formed; and if all three different dyes are utilized, a neutral image is formed.

Rupturable materials that can be used to prepare the pod The pods were constructed as shown in the drawings, FIGS. l4, except that the single pod has only one compartment. The sheet materials utilized to form the multicornpartrnent pods can be made of sheet materials such as a cellulose ester, polyethylene terephthalate, polyethylene, polypropylene sheets, or foils which are themselves water-vapor impermeable and unaffected by alkaline environments or which may be rendered thus by a suitable coating over the surface of the sheet material. The closures may be made by heat sealing. Examples of other auxiliary developing agents, which can be used in the place of methylphenyl hydroquinone, are listed in Weyerts and Salminen U.S. Patent application Ser. No. 73,390, filed Dec. 2, 1960.

EXAMPLE 2 Multiple-compartment pods of the type described herein can have utility in many transfer processes as well as other processing systems. For instance, the thickening agent can be separated from the alkali. This allows the use of thickening agents which would be degraded in alkaline solution, e.g., gelatin. A typical pod of this type has the following composition:

Compartment 1.-Gelatin solution+hydroquinone+ elon+sodium sulfite.

Compartment 2.-Water+sodium thiosulfate+sodium hydroxide.

EXAMPLE 3 Developing agents are more stable in neutral or acid solution than they are in alkaline solution. By using a twocompartment pod, the developing agent can be separated from the alkali. A typical pod of this type has the following composition:

Compartment 1.Hydrxyethyl cellulose solution-i-sodium hydroxide+sodium thiosulfate.

Compartment 2.Hydroxyethyl cellulose solution-l-hydroquinone-l-1-phenyl-3-pyrazolidone+sodium sulfite.

EXAMPLE 4 In monobath processing, it is sometimes advantageous to separate the stabilizing solution from the developing solution. This can be done by using a 2-compartment pod of the following composition:

Compartment 1.Carboxymethyl cellulose solution-{- hydroquinone-l-l phenyl-3-pyrazolidone+sodium sulfite +sodium hydroxide.

Compartment 2.Carboxymethyl cellulose solution+ ammonium thiocyanate.

EXAMPLE 5 In diffusion transfer processes, it is frequently desirable to use quaternary ammonium salts. Many of these, however, are not stable in alkaline solution. By using a twocompartment pod, however, the quaternary ammonium salt can be separated from the alkali. A typical pod of this type has the following composition:

Compartment 1.Carboxymethyl cellulose solution-I- lauryl pyridinium perchlorate.

Compartment 2.Carboxymethyl cellulose solution+ sodium hydroxide-l-sodium thiosulfate+chlorohydroquinone+ l-phenyl-3-pyrazolidone'+sodium sulfite.

EXAMPLE 6 A two-compartment pod with staggered closure edges is prepared containing in compartment 1, hydroxyethyl cellulose, water and sodium hydroxide. Compartment 2 contains hydroxyethyl cellulose, water, developing agent, silver halide solvent, development accelerators, antifoggants, and other specific addenda. This two-compartment pod was used for processing a black-and-white silver halide emulsion by rupturing the pod and causing the viscous solutions to flow across the exposed silver halide surface. Atthe same time as development is taking place, the developed emulsion is contacted against the light-sensitive receiving sheet containing nuclei to obtain a positive image by the diffusion-type photographic method. The result obtained was clear and of better quality than that obtained by combining the components in a single pod and permitting to stand for eight hours before developing the exposed emulsion.

The multiple-compartment pod may also be utilized in the conventional photographic processes. For instance, a monobath developer could be contained in one compartment of the pod and a stabilizer in a separate compartment. It will be apparent that this type of pod having the staggered breaking edge can be used for applying the developer solution for a first coating of the photographic element followed by the stabilizing coating for a successive coating.

EXAMPLE 7 It has been found useful to utilize a development arrestor in the color-transfer process described in Example 1. The development arrestor, Z-mercaptobenzoxazole, when placed in a third compartment over the two-compartments utilized in the pod described in Example 1, has a staggered breaking edge so that the developer components in the lower two compartments are released first to develop the negative image and is then followed by the development arrestor released from the uppermost compartment which halts the development reaction. The use of the development arrestor to halt the development reaction results in final color prints of higher maximum density than those obtained in a control process which does not contain the development arrestor.

Certain other materials have also been found useful when incorporated into the staggered-edge third compartment previously described or when used separately in an additional staggered-edge compartment. Thus UV absorbers such as 2(2-hydroxy-5,5'-t-octyl)-phenyl benzotriazole or 3-cetyl-2-phenylimino-S-benzalthiazolidone or the stabilizers, such as tannic acid, formaldehyde-napthalene sulfonic acid condensation produce or polyvinyl pyrrolidone, are finally released from an uppermost compartment and are migrated to the receiver sheet with the effect of stabilizing the final image obtained thereon in the known manner.

An additional improvement may be obtained in the process by the use of a surface active agent, such as sodium cetyl sulfate or the like, in an upppermost staggerededge compartment either in conjunction with one or more of the materials described above or in an individual compartment. Thus, the surface active agent would not influence the development reaction, its arrestation or the migration of the stabilizer but is finally released between the negative element and the contiguous receiving sheet and facilitates their separation.

The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.

I claim:

1. A liquid-carrying container comprising a pod having lateral compartment separators forming a plurality of compartments in a superposed position with each compartment having a bottom wall, a top wall, edge closures, an anterior closure and a posterior closure, the bottom walls and top walls of the compartments being substantially larger in area than the areas of the side closures, anterior closure or posterior closure, each compartment below the top compartment having the anterior closure extending laterally beyond the anterior closure of the next uppermost compartment, each compartment below the top compartment having the posterior closure extending laterally to or beyond the posterior closure of the next uppermost compartment, and each compartment having a bottom wall and a top wall larger in area than the respective bottom wall and top wall of the next uppermost compartment.

2. A container of claim 1 in which the anterior closure of each compartment is weaker than the edge closures of the posterior closure of the said compartment whereby it is adapted to be opened along the anterior closure by compression applied to the container, the compartments being opened in sequence beginning with the lowermost compartment to discharge the liquid in a thin continuous layer substantially over the overall length of said container.

3. A photographic product capable of forming transfer prints in conjunction with a photosensitive silver halide element, said product comprising said container of claim 2 with at least two interior compartments with means for holding liquid in the said compartments and a sheet support upon which said container is mounted, said sheet support providing an image receiving area adjacent to said container onto which the said liquids are flowed in a thin layer directly from said compartments, said liquids con taining alkaline material, silver halide developing agents, and a silver halide solvent, said liquids being sufiicient in amount and being so located to said image receiving area that the flowing of said liquids over said area disperses said substances throughout said area in adequate quantity to participate in the formation of a transfer print of a latent image in an area of a contiguous silver halide element equivalent to said image receiving area.

4. A container of claim 2 wherein said container has two adjacent compartments which have at least one common wall.

5. A photographic product of claim 3 wherein said container has two compartments.

6. A photographic product of claim 3 in which the liquid in one compartment contains a dihydroxybenzene developing agent, and the liquid in at least one of the compartments contains alkali, a film-forming material, a stabilizer and an onium salt.

7. A photographic product of claim 3 in which the liquid in one compartment contains 4-methyl phenyl hydroquinone and the liquid in the other compartment contains sodium hydroxide, benzotriazole, hydroxyethyl cellulose and B-benzyl-a-picolinium bromide.

8. A photographic product of claim 5 in which the liquid in one compartment contains hydroquinone and elon and the liquid in the other compartment contains sodium thiosulfate and sodium hydroxide.

9. A photographic product of claim 5 in which the liquid in one compartment comprises sodium thiosulfate and sodium hydroxide and the liquid in the other compartment comprises hydroquinone and 1-phenyl-3-pyrazolidone.

10. A photographic product of claim 5, in which the liquid in one compartment comprises ammonium thiocyanate and sodium hydroxide and the liquid in the other compartment comprises hydroquinone and 1-phenyl-3- pyrazolidone.

11. A photographic product of claim 5, in which the liquid in one compartment comprises lauryl pyridinium perchlorate and the liquid in the other compartment comprises chlorohydroquinone and l-phenyl-3-pyrazolidone sodium thiosulfate and sodium hydroxide.

12. The method of producing a visible positive image of the subject matter of a latent image contained in a predetermined area of a silver halide layer of a photosensitive sheet material, which method comprises locating a viscous liquid processing agent in a container of claim 2 having more than one compartment containing processing agents adapted to discharge said processing agents on one side only of said photosensitive sheet material in sufficient quantity to provide all the liquid for the development of said latent image, spreading said processing agents in a r layer between said photosensitive sheet material and another sheet material by applying pressure to the outer surfaces of said sheet materials, the portions of said outer surfaces subjected to said pressure remaining dry during said pressure application, liquid from said processing agents being absorbed by said photosensitive sheet material and, during absorption, distributing throughout said area of said photosensitive layer processing agents, including an alkaline material, developer for the silver halide and a silver halide solvent, capable of forming a soluble silver complex with the undeveloped silver halide, the development of said latent image producing an imagewise distribution of said soluble silver complex throughout the liquid of said processing agent, and retaining said sheet materials in their superposed condition until there is transported from the photosensitive layer a quantity of said soluble silver complex sufficient to form said positive image in a stratum of the lamination.

13. The method of claim 12 in which said container has two compartments.

References Cited UNITED STATES PATENTS 2,497,212 2/1950 Donofrio 1856 2,750,075 6/1956 Land et al. 22294 2,992,102 7/1961 Land 9629 3,030,207 4/1962 Land 9629 3,146,102 7/1964 Weyerts et al. 96-3 2,603,565 7/1952 Land 95-88 3,020,155 2/1962 Yackel et al 9629 I. TRAVIS BROWN, Acting Primary Examiner.

NORMAN G. TORCHIN, Examiner.

J. P. BRAMMER, Assistant Examiner. 

